Molybdenum-doped zinc/cobalt oxide electrocatalyst for hydrogen production

Abstract

An electrode includes an electrically conductive substrate and a layer of a molybdenum-doped zinc/cobalt oxide (ZnCo.sub.2-xMo.sub.xO.sub.4). The surface of the electrically conductive substrate is at least partially covered by the layer of ZnCo.sub.2-xMo.sub.xO.sub.4, where x is a positive number equal to or less than about 0.1, and the layer of the ZnCo.sub.2-xMo.sub.xO.sub.4 includes spherical-shaped particles. The electrode has a Tafel slope from 75 millivolts per second (mV/s) to 115 mV/s, and a potential of 0.27 to 0.30 volts relative to the reversible hydrogen electrode (V.sub.RHE) at a current density of about 50 mA/cm.sup.2 for a duration of at least 40 hours.

Claims

1. An electrode, comprising: an electrically conductive substrate; and a layer of a molybdenum-doped zinc/cobalt oxide (ZnCo.sub.2-xMo.sub.xO.sub.4) at least partially covering a surface of the electrically conductive substrate; wherein x is a positive number equal to or less than about 0.1; and wherein the layer of the ZnCo.sub.2-xMo.sub.xO.sub.4 comprises spherical shaped particles.

2. The electrode of claim 1, wherein the electrically conductive substrate comprises an indium tin oxide (ITO) glass, a fluorine dope tin oxide (FTO) glass, a silicone substrate, a graphite substrate, and a glassy carbon (GC) substrate.

3. The electrode of claim 1, wherein the electrically conductive substrate is a glassy carbon substrate.

4. The electrode of claim 1, wherein the spherical shaped particles of the ZnCo.sub.2-xMo.sub.xO.sub.4 have an average particle size of 2 micrometers (m) to 10 m.

5. The electrode of claim 1, wherein the spherical shaped particles of the ZnCo.sub.2-xMo.sub.xO.sub.4 comprise a porous matrix of interconnected nanoneedles, and wherein the interconnected nanoneedles have an average width of from 0.1 nanometers (nm) to 3 nm.

6. The electrode of claim 1, wherein the spherical shaped particles of the ZnCo.sub.2-xMo.sub.xO.sub.4 are aggregated.

7. The electrode of claim 1, wherein x is 0.06, and wherein the electrode has an overpotential of about 195 millivolts (mV) relative to the reversible hydrogen electrode (mV.sub.RHE) at a current density of about 10 milliamperes per square centimeter (mA/cm.sup.2).

8. The electrode of claim 1, wherein x is 0.06, and wherein the electrode has an overpotential of about 280 mV.sub.RHE at a current density of about 50 mA/cm.sup.2.

9. The electrode of claim 1, having a Tafel slope of from 75 millivolts per second (mV/s) to 115 mV/s.

10. The electrode of claim 1, wherein x is 0.06, and wherein the electrode has a Tafel slope of about 81.4 mV/s.

11. The electrode of claim 1, having a potential of from 0.27 to 0.30 volts relative to the reversible hydrogen electrode (V.sub.RHE) at a current density of about 50 mA/cm.sup.2 for a duration of at least 40 hours.

12. A method of making the electrode of claim 1, comprising preparing the ZnCo.sub.2-xMo.sub.xO.sub.4 by: mixing and dissolving a Zn salt, a Co salt, a Mo salt, and urea in a solvent to form a mixture; heating the mixture at a temperature of about 120 degrees Celsius ( C.) to form a precursor compound in the form of a precipitate; and separating the precursor compound from the mixture and calcining at a temperature of from 250 to 450 C.

13. The method of claim 12, wherein the Zn salt comprises zinc acetylacetonate, zinc sulfate, zinc acetate, zinc citrate, zinc iodide, zinc chloride, zinc perchlorate, zinc nitrate, zinc phosphate, zinc triflate, zinc bis(trifluoromethanesulfonyl)imide, zinc tetrafluoroborate, zinc bromide, and/or its hydrate.

14. The method of claim 12, wherein the Co salt comprises cobalt acetylacetonate, cobalt sulfate, cobalt acetate, cobalt citrate, cobalt iodide, cobalt chloride, cobalt perchlorate, cobalt nitrate, cobalt phosphate, cobalt triflate, cobalt bis(trifluoromethanesulfonyl)imide, cobalt tetrafluoroborate, cobalt bromide, and/or its hydrate.

15. The method of claim 12, wherein the Mo salt is ammonium molybdate.

16. The method of claim 12, wherein the calcining the precursor compound is performed at a temperature of about 350 C. for 1 to 6 hours.

17. The method of claim 12, further comprising: mixing the ZnCo.sub.2-xMo.sub.xO.sub.4, one or more solvents, and a sulfonated polymer to form a slurry; and drop-casting the slurry onto a surface of the GC substrate to form a sample; and drying the sample.

18. The method of claim 17, wherein the ZnCo.sub.2-xMo.sub.xO.sub.4 is present on the surface of the GC substrate in an amount of from 0.25 milligrams per square centimeter (mg/cm.sup.2) to 0.32 mg/cm.sup.2 of a surface area of the GC substrate in contact with the slurry.

19. A method for electrochemical water splitting, comprising: applying a potential between a counter and a working electrode in an electrochemical cell containing an electrolyte to form hydrogen and oxygen; and separately collecting H.sub.2-enriched gas and O.sub.2-enriched gas; wherein the working electrode comprises the electrode of claim 1; and wherein the electrolyte comprising an aqueous solution of a base at a concentration of 0.05 molar (M) to 5 M.

20. The method of claim 19, wherein the base is at least one selected from the group consisting of sodium hydroxide (NaOH), potassium hydroxide (KOH), lithium hydroxide (LiOH), barium hydroxide (Ba(OH).sub.2), and calcium hydroxide (Ca(OH).sub.2).

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) A more complete appreciation of this disclosure and many of the attendant advantages thereof will be readily obtained as the same becomes better understood by reference to the following detailed description when considered in connection with the accompanying drawings, wherein:

(2) FIG. 1 is a flowchart depicting a method of making an electrode, according to certain embodiments.

(3) FIG. 2A is an image of an X-ray powder pattern of molybdenum-doped zinc/cobalt oxide (ZnCo.sub.2-xMo.sub.xO.sub.4 (x0.10)), according to certain embodiments.

(4) FIG. 2B is an enlarged image of an X-ray powder pattern of ZnCo.sub.2-xMo.sub.xO.sub.4 (x0.10), according to certain embodiments.

(5) FIGS. 3A-3C is a scanning electron microscopy (SEM) image of ZnCo.sub.2-xMo.sub.xO.sub.4 at different magnifications, according to certain embodiments.

(6) FIG. 4A shows energy-dispersive X-ray (EDX) spectra of ZnCo.sub.2-xMo.sub.xO.sub.4 (x=0.06), according to certain embodiments.

(7) FIG. 4B shows transmission electron microscopy (TEM) of ZnCo.sub.2-xMo.sub.xO.sub.4 (x=0.06), according to certain embodiments.

(8) FIG. 4C is a high-resolution transmission electron microscopy (HR-TEM) image of ZnCo.sub.2-xMo.sub.xO.sub.4 (x=0.06), according to certain embodiments.

(9) FIG. 5A shows X-ray photoelectron spectroscopy (XPS) analysis of ZnCo.sub.2-xMo.sub.xO.sub.4 (x=0.06), according to certain embodiments.

(10) FIG. 5B shows Co 2p in an XPS analysis of ZnCo.sub.2-xMo.sub.xO.sub.4 (x=0.06), according to certain embodiments.

(11) FIG. 5C shows Mo 3d in an XPS analysis of ZnCo.sub.2-xMo.sub.xO.sub.4 (x=0.06), according to certain embodiments.

(12) FIG. 5D shows Zn 2p in an XPS analysis of ZnCo.sub.2-xMo.sub.xO.sub.4 (x=0.06), according to certain embodiments.

(13) FIG. 5E shows O is in an XPS analysis of ZnCo.sub.2-xMo.sub.xO.sub.4 (x=0.06), according to certain embodiments.

(14) FIG. 6A is a graph of linear sweep voltammetry (LSV) polarization curves of ZnCo.sub.2-xMo.sub.xO.sub.4 (x0.10) electrocatalyst measured in 1.0 molar (M) potassium hydroxide (KOH), solution, according to certain embodiments.

(15) FIG. 6B is a overpotential () histogram at 10 milliamperes per square centimeter (mA cm.sup.2) and 50 mA cm.sup.2 of ZnCo.sub.2-xMo.sub.xO.sub.4 (x0.10) electrocatalyst measured in 1.0 M KOH solution, according to certain embodiments.

(16) FIG. 6C shows a Tafel plot of ZnCo.sub.2-xMo.sub.xO.sub.4 (x0.10) electrocatalyst measured in 1.0 M KOH solution, according to certain embodiments.

(17) FIG. 7A is a cyclic voltammetry (CV) curve of ZnCo.sub.2-xMo.sub.xO.sub.4 (x=0.06) electrocatalyst, according to certain embodiments.

(18) FIG. 7B shows double layer capacitance (Cdl) of ZnCo.sub.2-xMo.sub.xO.sub.4 (x=0.06) electrocatalyst, according to certain embodiments.

(19) FIG. 7C is a histogram of electrochemical surface area (ECSA) of ZnCo.sub.2-xMo.sub.xO.sub.4 (x=0.06) electrocatalyst, according to certain embodiments.

(20) FIG. 7D is a histogram of specific current activity (j.sub.SA) of ZnCo.sub.2-xMo.sub.xO.sub.4 (x0.10) electrocatalysts, according to certain embodiments.

(21) FIG. 8A shows LSV curves normalized against ECSA of the ZnCo.sub.2-xMo.sub.xO.sub.4 catalysts (x=0.0, 0.02, 0.04, 0.06, 0.08, and 0.1), according to certain embodiments.

(22) FIG. 8B is a histogram of normalized current against ECSA at 0.3 V overpotential of the ZnCo.sub.2-xMo.sub.xO.sub.4 electrodes (x=0.0, 0.02, 0.04, 0.06, 0.08, and 0.1), according to certain embodiments.

(23) FIG. 8C is a histogram showing number of active sites (N) for ZnCo.sub.2-xMo.sub.xO.sub.4 (x0.10) electrodes measured in 1.0 M KOH solution, according to certain embodiments.

(24) FIG. 9A shows electrochemical impedance spectroscopy (EIS) spectra of ZnCo.sub.2-xMo.sub.xO.sub.4 electrocatalysts, according to certain embodiments.

(25) FIG. 9B is a charge transfer resistance (R.sub.ct) histogram of the ZnCo.sub.2-xMo.sub.xO.sub.4 electrodes (x=0.0, 0.02, 0.04, 0.06, 0.08, and 0.1), according to certain embodiments.

(26) FIG. 9C is an exchange current density (I.sub.ex) histogram of the ZnCo.sub.2-xMo.sub.xO.sub.4 electrodes (x=0.0, 0.02, 0.04, 0.06, 0.08, and 0.1), according to certain embodiments.

(27) FIG. 9D is an illustration of an equivalent circuit used to fit the Nyquist plot of ZnCo.sub.2-xMo.sub.xO.sub.4(x0.10) electrocatalyst, according to certain embodiments.

(28) FIG. 10A is a graph of overlaid initial and final LSV showing the curves after 1000.sup.th consecutive LSV scans for ZnCo.sub.2-xMo.sub.xO.sub.4 (x=0.06) electrocatalyst, according to certain embodiments.

(29) FIG. 10B is a graph of multi-step chronopotentiometry showing the curve within the current density range 10-50 mA cm.sup.2 for ZnCo.sub.2-xMo.sub.xO.sub.4 (x=0.06) electrocatalyst, according to certain embodiments.

(30) FIG. 10C is graph of potential-time dependent showing the curve at 50 mA cm.sup.2 current density for ZnCo.sub.2-xMo.sub.xO.sub.4 (x=0.06) electrocatalyst, according to certain embodiments.

(31) FIG. 10D shows a comparison of the Nyquist plot at 0.3 VRHE for the ZnCo.sub.2-xMo.sub.xO.sub.4 (x=0.06) electrocatalyst before and after the stability test in a 1.0 M KOH solution, according to certain embodiments.

(32) FIG. 11A shows XRD spectra for ZnCo.sub.2-xMo.sub.xO.sub.4 (x=0.06) electrocatalyst after the stability test, according to certain embodiments.

(33) FIG. 11B is a FE-SEM image of the ZnCo.sub.2-xMo.sub.xO.sub.4 (x=0.06) electrocatalyst after the stability test, according to certain embodiments.

(34) FIG. 12A is an illustration of unit cells for MSOMCs-H.sup.I, according to certain embodiments.

(35) FIG. 12B is an illustration of unit cells for MSOMCs-W.sup.I, according to certain embodiments.

(36) FIG. 13A is a graph of density of states (DOS.sub.) for the PSOMCs-H, projected to the Mo dopants within MSOMCs-H.sup.I and MSOMCs-H.sup.II, according to certain embodiments.

(37) FIG. 13B is a graph of partial density of states (PDOS.sub.) for the MSOMCs-H.sup.I and MSOMCs-H.sup.II, projected to the Mo dopants within MSOMCs-H.sup.I and MSOMCs-H.sup.II, according to certain embodiments.

(38) FIG. 13C is an image of cut-plane view of electron density for the PSOMCs-W, according to certain embodiments.

(39) FIG. 13D is an image of cut-plane view of electron density for the MSOMCs-W.sup.I, according to certain embodiments.

DETAILED DESCRIPTION

(40) When describing the present disclosure, the terms used are to be construed in accordance with the following definitions, unless a context dictates otherwise.

(41) Embodiments of the present invention will now be described more fully hereinafter with reference to the accompanying drawings wherever applicable, in that some, but not all embodiments of the disclosure are shown.

(42) In the drawings, like reference numerals designate identical or corresponding parts throughout the several views. Further, as used herein, the words a, an and the like generally carry a meaning of one or more, unless stated otherwise.

(43) Furthermore, the terms approximately, approximate, about, and similar terms generally refer to ranges that include the identified value within a margin of 20%, 10%, or preferably 5%, and any values therebetween.

(44) The use of the terms include, includes, including, have, has, or having should be generally understood as open-ended and non-limiting unless specifically stated otherwise.

(45) As used herein, nanoparticles are particles having a particle size of 1 nm to 500 nm within the scope of the present invention.

(46) As used herein, particle size and pore size may be thought of as the lengths or longest dimensions of a particle and of a pore opening, respectively.

(47) As used herein, the term room temperature refers to a temperature range of 25 C.3 C. in the present disclosure.

(48) As used herein, the term electrode refers to an electrical conductor used to contact a non-metallic part of a circuit, such as a semiconductor, an electrolyte, a vacuum, or air.

(49) As used herein, the term current density refers to the amount of electric current traveling per unit cross-section area.

(50) As used herein, the term Tafel slope refers to the relationship between the overpotential and the logarithmic current density.

(51) As used herein, the term electrochemical cell refers to a device capable of either generating electrical energy from chemical reactions or using electrical energy to cause chemical reactions.

(52) As used herein, the term water splitting refers to the chemical reaction in which water is broken down into oxygen and hydrogen.
2H.sub.2O.fwdarw.2H.sub.2+O.sub.2

(53) As used herein, the term overpotential refers to the difference in potential that exists between a thermodynamically determined reduction potential of a half-reaction and the potential at which the redox event is experimentally observed. The term is directly associated with a cell's voltage efficacy. In an electrolytic cell, the occurrence of overpotential implies that the cell needs more energy as compared to that thermodynamically expected to drive a reaction. The quantity of overpotential is specific to each cell design and varies across cells and operational conditions, even for the same reaction. Overpotential is experimentally measured by determining the potential at which a given current density is reached.

(54) The present disclosure is intended to include all hydration states of a given compound or formula, unless otherwise noted or when heating a material.

(55) In addition, the present disclosure is intended to include all isotopes of atoms occurring in the present compounds and complexes. Isotopes include those atoms having the same atomic number but different mass numbers. By way of general example, and without limitation, isotopes of hydrogen include deuterium and tritium. Isotopes of naturally occurring nickel .sup.28Ni include .sup.58Ni, .sup.60Ni, .sup.61Ni, .sup.62Ni, and .sup.64Ni. Isotopes of oxygen include .sup.16O, .sup.17O, and .sup.18O, isotopes of cobalt (Co) are .sup.56Co, .sup.57Co, .sup.58Co, and .sup.60Co, and isotopes of molybdenum includes .sup.81Mo, .sup.82Mo, .sup.83Mo, .sup.84Mo, .sup.85Mo, .sup.86Mo, .sup.87Mo, .sup.88Mo, .sup.89Mo, .sup.90Mo, .sup.91Mo, .sup.92Mo, .sup.93Mo, .sup.94Mo, .sup.95Mo, .sup.96Mo, .sup.97Mo, .sup.98Mo, .sup.99Mo, .sup.100Mo, .sup.101Mo, .sup.102Mo, .sup.103Mo, .sup.104Mo, .sup.105Mo, .sup.106Mo, .sup.107Mo, .sup.108Mo, .sup.109Mo, .sup.110Mo, .sup.111Mo, .sup.112Mo, .sup.113Mo, .sup.114Mo, .sup.115Mo, .sup.116Mo, .sup.117Mo, .sup.118Mo, and .sup.119Mo. Isotopically-labeled compounds of the disclosure may generally be prepared by conventional techniques known to those skilled in the art or by processes analogous to those described herein, using an appropriate isotopically-labeled reagent in place of the non-labeled reagent otherwise employed.

(56) Aspects of the present disclosure are directed to transition metal-based electrocatalysts, ZnCo.sub.2-xMo.sub.xO.sub.4 (x0.10), for hydrogen evolution reaction (HER) and their use for the water-splitting process. The electrocatalysts of the present disclosure were used as electrodes and were evaluated for their potential in the water-splitting process. The ZnCo.sub.2-xMo.sub.xO.sub.4 (x=0.06) electrocatalyst exhibited exceptional HER activity as evidenced by 195 mV overpotential, Tafel slope 81.4 mV s.sup.1, and high stability for 40 hours. The electrocatalyst of the present disclosure uses low-metal-cost materials for efficient and durable HER electrocatalysts.

(57) The electrode of the present disclosure includes an electrically conductive substrate and a layer of a molybdenum-doped zinc/cobalt oxide (ZnCo.sub.2-xMo.sub.xO.sub.4) that at least partially covers the surface of the electrically conductive substrate. The electrically conductive substrate includes one selected from an indium tin oxide (ITO) glass, a fluorine dope tin oxide (FTO) glass, a silicone substrate, a graphite substrate, and a glassy carbon (GC) substrate. In a preferred embodiment, the electrically conductive substrate is a GC substrate. The GC substrate may have a thickness in a range of about 10 micrometers (m) to 140 m, for example, ranging from about 20 m to about 120 m, from about 50 m to about 100 m, from about 70 m to about 95 m, or from about 85 m to about 90 m, including all ranges and sub-ranges therebetween.

(58) The ZnCo.sub.2-xMo.sub.xO.sub.4 particles may be dispersed on the surface of the substrate using a technique like the drop-casting, spray coating, spin coating, dip coating, hydrothermal growth, or aerosol-assisted chemical vapor deposition (AACVD), preferably drop-casting. The ZnCo.sub.2-xMo.sub.xO.sub.4 particles are distributed on the surface of the GC substrate such that at least 50%, preferably 55%, preferably 60%, preferably 65%, preferably 70%, preferably 75%, preferably 80%, preferably 85%, preferably 90%, and preferably >95% of the syrface of the substrate is covered with ZnCo.sub.2-xMo.sub.xO.sub.4 particles.

(59) The x in ZnCo.sub.2-xMo.sub.xO.sub.4 is a positive number equal to or less than about 0.1. In some embodiments, the x is about 0.02, about 0.04, about 0.06, and about 0.08. In a preferred embodiment, x is 0.06. The ZnCo.sub.2-xMo.sub.xO.sub.4 particles are spherical in shape and have an average particle size of 2 micrometers (m) to 10 m, preferably 2 m, preferably 3 m, prefearbly 4 m, prefearbly 5 m. The spherical-shaped particles of the ZnCo.sub.2-xMo.sub.xO.sub.4 include a porous matrix of interconnected nanoneedles, with an average width of 0.1 nanometers (nm) to 3 nm. In some embodiments, the spherical-shaped particles of the ZnCo.sub.2-xMo.sub.xO.sub.4 are aggregated.

(60) In alternate embodiments, the ZnCo.sub.2-xMo.sub.xO.sub.4 particles may have different morphologies, such as nanowires, nanorods, nanocrystals, nanorectangles, nanotriangles, nanopentagons, nanohexagons, nanoprisms, nanodisks, nanocubes, nanoribbons, nanoblocks, nanobeads, nanotoroids, nanodiscs, nanobarrels, nanogranules, nanowhiskers, nanoflakes, nanofoils, nanopowders, nanoboxes, nanostars, tetrapods, nanobelts, nano-urchins, nanoflowers, etc. and mixtures thereof.

(61) The ZnCo.sub.2-xMo.sub.xO.sub.4 particles, when x=0.06, preferably comprises 20-35 wt. % of oxygen, preferably 21-34 wt. %, preferably 22-33 wt. %, preferably 23-32 wt. %, preferably 24-31 wt. %, prefearbly 25-30 wt. %, preferably 26-29 wt. %, preferably 27-29 wt. %, preferably 28-29 wt. %; 40-50 wt. % of cobalt, prefearbly 41-49 wt. %, preferably 42-48 wt. %, preferably 43-47 wt. %, preferably 44-47 wt. %, prefearbly 46-47 wt. % of oxygen; preferably 20-30 wt. % of zinc, preferably 21-27 wt. %, preferably 22-25 wt. %, preferably 23-24 wt. % of zinc; and 1-5 wt. % of molybdenum, preferably 1.5-3 wt. %, preferably 1.5-2 wt. % of molybdenum.

(62) Referring to FIG. 1, a schematic flow diagram of a method 50 of making ZnCo.sub.2-xMo.sub.xO.sub.4 is illustrated. The order of the steps of the method 50 is not intended to be construed as a limitation, and any number of the described method steps may be combined in any order to implement the method 50. Additionally, individual steps may be removed or skipped from the method 50 without departing from the spirit and scope of the present disclosure.

(63) At step 52, the method 50 includes mixing and dissolving a Zn salt, a Co salt, a Mo salt, and urea in a solvent to form a mixture. In some embodiments, the cobalt salt includes one or more selected from cobalt acetylacetonate, cobalt sulfate, cobalt acetate, cobalt citrate, cobalt iodide, cobalt chloride, cobalt perchlorate, cobalt nitrate, cobalt phosphate, cobalt triflate, cobalt bis(trifluoromethanesulfonyl)imide, cobalt tetrafluoroborate, cobalt bromide, and/or its hydrate. Preferably, the cobalt in the cobalt salt has a +2 oxidation state, though in an alternative embodiment, cobalt having a different oxidation state, such as +3, may be used. In one embodiment, the cobalt of the cobalt salt consists essentially of cobalt in a +2 oxidation state. As defined here, the cobalt consisting essentially of cobalt in a +2-oxidation state means that at least 95 wt. %, preferably at least 99.wt %, more preferably at least 99.5 wt. % of the cobalt, has a +2 oxidation state relative to the total weight of the cobalt. Preferably, the cobalt salt may be in any hydration state; for instance, Co(NO.sub.3).sub.2 includes both Co(NO.sub.3).sub.2 and Co(NO.sub.3).sub.2.Math.6H.sub.2O. In a preferred embodiment, the cobalt salt is Co(NO.sub.3).sub.2. Suitable examples of the zinc salt include one or more selected from zinc acetylacetonate, zinc sulfate, zinc acetate, zinc citrate, zinc iodide, zinc chloride, zinc perchlorate, zinc nitrate, zinc phosphate, zinc triflate, zinc bis(trifluoromethanesulfonyl)imide, zinc tetrafluoroborate, zinc bromide, and/or its hydrate. Suitable examples of Mo salt include, but not limited to, ammonium heptamolybdate(VI), ammonium heptamolybdate(VI) tetrahydrate, ammonium molybdate(VI), ammonium phosphomolybdate, ammonium tetrathiomolybdate, sodium molybdate(VI), lithium molybdate(VI), molybdenum(VI) dichloride dioxide, and mixtures and hydrates thereof. In certain embodiments, a molybdenum salt having a different oxidation state, such as +2 (e.g., molybdenum(H) carboxylates), +3 (e.g., molybdenum(III) chloride), +4 (e.g., molybdenum(IV) carbonate), and +5 (e.g., molybdenum(V) chloride). In a preferred embodiment, the Mo salt is ammonium molybdate. The weight ratio of the cobalt salt to the zinc salt is in the range of 1:5 to 5:1, preferably 1:4 to 4:1, preferably 1:3 to 3:1, preferably 1:2 to 2:1, preferably 1:1. In a most preferred embodiment, the weight ratio of the Co salt to the Zinc salt is 2:1. The mixing may be preferably be carried out at room temperature, for 10-60 minutes, preferably 20-50 minutes, preferably 20-30 minutes, preferably 20 minutes.

(64) The Co salt, Zn salt, Mo salt, and urea are mixed in a solvent to form a mixture. Mixing may occur via stirring, shaking, swirling, sonicating, blending, or by otherwise agitating a mixture. In one embodiment, the mixture is stirred by a magnetic stirrer or an overhead stirrer. In another embodiment, the mixture is left to stand (i.e. not stirred). The molar concentration of urea is in the range of 1-5 M, preferably 1-3 M, preferably 1 M. The solvent may be water, an alcohol such as methanol and ethanol, or a mixture thereof. In one or more embodiments, the solvent is water, preferably deionized or distilled water.

(65) At step 54, the method 50 includes heating the mixture at a temperature of about 120 degrees Celsius ( C.) to form a precursor compound in the form of a precipitate. The mixture may be hydrothermally treated to form a precipitate. In one embodiment, the mixture is hydrothermally treated via heating in an autoclave at 50-150 C., preferably 120 C., for 6-24 hours, preferably 6-12 hours, more preferably 8 to produce the precursor compound. An external heat source, such as an oven, a heating mantle, a water bath, or an oil bath, may be employed to heat the mixture.

(66) At step 56, the method 50 includes separating the precursor compound from the mixture and calcining at a temperature from 250 to 450 C. The precursor compound may be separated from the precipitate via centrifugation/filtration. After separation, the precursor compound may be washed with water/alcohol (ethanol) and calcined to form the ZnCo.sub.2-xMo.sub.xO.sub.4 particles. The precursor compound was further calcined at a temperature range of 250 to 450 C., preferably 300-400 C., preferably 350-375 C., or about 300 C. for 0.5-8 hours, preferably 1-6 hours, preferably 2-4 hours, or about 3 hours to form the ZnCo.sub.2-xMo.sub.xO.sub.4 particles (electrocatalyst). Calcination can be carried out within shaft furnaces, rotary kilns, multiple hearth furnaces, and/or fluidized bed reactors. In some embodiments, the precursor compound is calcined at a temperature of about 350 C. for 1 to 6 hours to obtain ZnCo.sub.2-xMo.sub.xO.sub.4. The ZnCo.sub.2-xMo.sub.xO.sub.4 particles obtained may be used to prepare the electrode via the steps described below.

(67) At step 58, the method 50 includes mixing the ZnCo.sub.2-xMo.sub.xO.sub.4, one or more solvents, and a sulfonated polymer to form a slurry. The solvents may be one or more selected from water, ethanol, isopropyl alcohol, acetone, N, N-dimethylacetamide, 1-methyl-2-pyrrolidinone, 1,3-dioxolane, 2-methoxy ethanol, or benzyl alcohol. In a preferred embodiment, the solvent includes a combination of water and ethanol, with water and ethanol preferably in a v/v ratio of 1:5 to 5:1, preferably 4:1 to 1:4, preferably 4:1. The sulfonated polymer serves as a binder that binds the ZnCo.sub.2-xMo.sub.xO.sub.4 particles to a substrate. Suitable examples of sulfonated polymer include one or more selected from sulfonated tetrafluoroethylene-based fluoropolymer-copolymer, sulfonated polyetheretherketone (SPEEK), sulfonated polysulfone (SPSF), sulfonated polysulfideulfone (SPSS). In a preferred embodiment, the sulfonated polymer is Nafion (sulfonated tetrafluoroethylene-based fluoropolymer-copolymer). Optionally, other binders may be used as wellfor example, poly(diallyl amine), diallyl ketone, diallyl amine, styryl sulfonate, vinyl lactam, laponite, polygorskites (such as attapulgite, sepiolite), and combinations thereof.

(68) At step 60, method 50 includes drop-casting the slurry onto the surface of the GC (glassy carbon) substrate to form a sample. Optionally, other substrates such as stainless steel, aluminum, nickel, copper, platinum, zinc, tungsten, titanium, and carbon may be used as well. The ZnCo.sub.2-xMo.sub.xO.sub.4 particles are drop-casted on the GC substrate such that 0.25 milligrams per square centimeter (mg/cm.sup.2) to 0.32 mg/cm.sup.2 of a surface area of the GC substrate in contact with the slurry. Drop casting is a typically used for forming small coatings on small surfaces. It requires only a small amount of solvent. In this method, the slurry is dripped onto the substrate as drops and allowed to dry without spreading. Alternate techniques for depositing the catalyst on the substrate include spray coating, spin coating, and dip coating.

(69) At step 62, the method 50 includes drying the sample, preferably at room temperature for 1-6 hours, preferably 2-4 hours, preferably 3 hours, to form the electrode.

(70) The electrode of the present disclosure has a potential of 0.27 to 0.30 volts relative to the reversible hydrogen electrode (V.sub.RHE) at a current density of about 50 mA/cm.sup.2 for a duration of at least 40 hours. In some embodiments, the electrode including ZnCo.sub.2-xMo.sub.xO.sub.4, when x is 0.06, has an overpotential of about 195 millivolts (mV) relative to the reversible hydrogen electrode (mV.sub.RHE) at a current density of about 10 milliamperes per square centimeter (mA/cm.sup.2). In some embodiments, when x is 0.06, the electrode has an overpotential of about 280 mV.sub.RHE at a current density of about 50 mA/cm.sup.2. The electrode has a Tafel slope of from 75 millivolts per second (mV/s) to 115 mV/s. In a specific embodiment, when x is 0.06 in ZnCo.sub.2-xMo.sub.xO.sub.4, the electrode has a Tafel slope of about 81.4 mV/s.

(71) A method of generating hydrogen via electrochemical water splitting with the electrode is described. The method includes applying a potential of 0.1 to 2.0 volts (V), preferably 0.2-1.9 V, preferably 0.3-1.8 V, preferably 0.4-1.7 V, preferably 0.5-1.6 V, preferably 0.6-1.5 V, preferably 0.7-1.4 V, preferably 0.8-1.3 V, preferably 0.9-1.2 V, and preferably 1.0-1.1 V, to an electrochemical cell. The electrochemical cell includes a counter electrode and an electrocatalyst (working electrode. In some embodiments, the counter electrode includes at least one of graphite and platinum. In alternate embodiments, the counter electrode is made from a material selected from the group consisting of platinum, gold, and carbon. In alternate embodiments, the counter electrode may contain an electrically-conductive material such as platinum, platinum-iridium alloy, iridium, titanium, titanium alloy, stainless steel, gold, cobalt alloy, and/or some other electrically-conductive material, where an electrically-conductive material as defined here is a substance with an electrical resistivity of at most 10.sup.6.Math.m, preferably at most 10.sup.7.Math.m, more preferably at most 10.sup.8.Math.m at a temperature of 20-25 C. The form of the counter electrode may be generally relevant only in that it needs to supply sufficient current to the electrolyte solution to support the current required for the electrochemical reaction of interest. The counter electrode material should thus be sufficiently inert to withstand the chemical conditions in the electrolyte solution, such as acidic or basic pH values, without substantially degrading during the electrochemical reaction. The counter electrode should preferably not leach out any chemical substance that interferes with the electrochemical reaction or might lead to undesirable electrode contamination. In a preferred embodiment, the counter electrode is graphite.

(72) In one embodiment, the electrochemical cell further includes a reference electrode in contact with the electrolyte solution. A reference electrode is an electrode that has a stable and well-known electrode potential. The high stability of the electrode potential is usually reached by employing a redox system with constant (buffered or saturated) concentrations of each relevant species of the redox reaction. A reference electrode may enable a potentiostat to deliver a stable voltage to the working electrode or the counter electrode. The reference electrode may be a standard hydrogen electrode (SHE), a normal hydrogen electrode (NHE), a reversible hydrogen electrode (RHE), a saturated calomel electrode (SCE), a copper-copper(II) sulfate electrode (CSE), a silver chloride electrode (Ag/AgCl), a pH-electrode, a palladium-hydrogen electrode, a dynamic hydrogen electrode (DHE), a mercury-mercurous sulfate electrode, mercury/mercuric oxide (Hg/HgO) electrode, or some other type of electrode. In a preferred embodiment, a reference electrode is an Ag/AgCl electrode. However, in some embodiments, the electrochemical cell does not include a third electrode.

(73) In some embodiments, the electrochemical cell is at least partially submerged in an electrolyte, preferably 50%, preferably 60%, or more preferably at least 70%. In some embodiments, the aqueous solution includes water and a base. The water may be tap water, distilled water, bidistilled water, deionized water, deionized distilled water, reverse osmosis water, and/or some other water. In some embodiments, the electrolyte includes the aqueous solution of the base at a concentration of 0.05-0.5 M, preferably 0.1-0.45 M, preferably 0.15-0.4 M, preferably 0.2-0.35 M, and preferably 0.25-0.3 M. In a preferred embodiment, the electrolyte includes the aqueous solution of a base at a concentration of 1 M. In some embodiments, the base is at least one selected from the group consisting of sodium hydroxide (NaOH), potassium hydroxide (KOH), lithium hydroxide (LiOH), barium hydroxide (Ba(OH).sub.2), calcium hydroxide (Ca(OH).sub.2). In an alternative embodiment, an organic base may be used, such as sodium acetate and potassium acetate. In a preferred embodiment, the base is KOH. Preferably, to maintain uniform concentrations and/or temperatures of the electrolyte solution, the electrolyte solution may be stirred or agitated during the step of the subjecting. The stirring or agitating may be done intermittently or continuously. This stirring or agitating may be done by a magnetic stir bar, a stirring rod, an impeller, a shaking platform, a pump, a sonicator, a gas bubbler, or some other device. Preferably, the stirring is done by an impeller or a magnetic stir bar.

(74) The method further includes separately collecting H.sub.2-enriched gas and O.sub.2-enriched gas. The oxygen may be generated by decomposing water into H.sub.2 and O.sub.2. In one embodiment, the space above each electrode may be confined to a vessel to receive or store the evolved gases from one or both electrodes. The collected gas may be further processed, filtered, or compressed. Preferably, the H.sub.2-enriched gas is collected above the cathode, and the O.sub.2-enriched gas is collected above the anode. The electrolytic cell, or an attachment, may be shaped so that the headspace above the working electrode is kept separate from the headspace above the reference electrode. In one embodiment, the H.sub.2-enriched gas and the O.sub.2-enriched gas are not 100 vol % H.sub.2 and 100 vol % O.sub.2, respectively. For example, the enriched gases may also include N.sub.2 from the air, water vapor, and other dissolved gases from the electrolyte solution. The H.sub.2-enriched gas may also include O.sub.2 from the air. The H.sub.2-enriched gas may include greater than 20 vol % H.sub.2, preferably greater than 40 vol % H.sub.2, more preferably greater than 60 vol % H.sub.2, and even more preferably greater than 80 vol % H.sub.2, relative to a total volume of the receptacle collecting the evolved H.sub.2 gas. The O.sub.2-enriched gas may include greater than 20 vol % O.sub.2, preferably greater than 40 vol % O.sub.2, more preferably greater than 60 vol % O.sub.2, and even more preferably greater than 80 vol % O.sub.2, relative to a total volume of the receptacle collecting the evolved O.sub.2 gas. In some embodiments, the evolved gases may be bubbled into a vessel, including water or some other liquid, and higher concentrations of O.sub.2 or H.sub.2 may be collected. In one embodiment, evolved O.sub.2 and H.sub.2, or H.sub.2-enriched gas and O.sub.2-enriched gas, may be collected in the same vessel.

(75) The electrocatalyst of the present disclosure may also be used in water-splitting reactions. In some embodiments, the electrocatalyst may also be used in the field of batteries, fuel cells, photochemical cells, water splitting cells, electronics, water purification, hydrogen sensors, semiconductors (such as field-effect transistors), magnetic semiconductors, capacitors, data storage devices, biosensors (such as redox protein sensors), photovoltaics, liquid crystal screens, plasma screens, touch screens, OLEDs, antistatic deposits, optical coatings, reflective coverings, anti-reflection coatings, and/or reaction catalysis.

EXAMPLES

(76) The following examples demonstrate molybdenum-doped zinc/cobalt oxide electrocatalyst as described herein. The examples are provided solely for illustration and are not to be construed as limitations of the present disclosure, as many variations thereof are possible without departing from the spirit and scope of the present disclosure.

Example 1: Chemicals

(77) Zinc nitrate (98.0%), cobalt (II) nitrate (98.0%), ammonium molybdate (99.0%), and urea were obtained from Sigma-Aldrich. The chemicals used are analytical grades and utilized with no additional purification.

Example 2: Preparation of Bare and Mo-Doped ZnCo.SUB.2.O.SUB.4

(78) The molybdenum-doped zinc/cobalt oxide (ZnCo.sub.2-xMo.sub.xO.sub.4 (x0.10)) was prepared by hydrothermal method followed by calcination processes. ZnCo.sub.2O.sub.4 was synthesized by mixing 2.98 grams (g) of zinc nitrate and 5.82 g of cobalt (II) nitrate with 1.0 M urea in 50 milliliters (mL) deionized (DI) water while stirring for 20 minutes at room temperature to form a solution. The solution was transferred to the 100 mL Teflon lined stainless-steel autoclave. The autoclave was closed and heated at 120 degrees Celsius ( C.) for 8 hours (h). The autoclave was then cooled to room temperature, and the powder from the solution was washed with DI water and ethanol and gathered by a centrifugation process. The resulting powder was dried at 60 C. overnight and calcinated at 350 C. in ambient environment for 3 h. Further ZnCo.sub.2-xMo.sub.xO.sub.4 (x0.10, where x=0.00, 0.02, 0.04, 0.06, 0.08, and 0.10) were prepared by adding a specific amount of ammonium molybdate following the same procedure.

Example 3: Physicochemical Characterization

(79) The lattice structural information of the ZnCo.sub.2-xMo.sub.xO.sub.4, (x0.10) phase was investigated using an X-ray diffractometer (XRD) (wavelength ()=1.54059 angstrom (A)). The morphology of ZnCo.sub.2-xMo.sub.xO.sub.4, was examined by transmission electron microscopy (TEM) and scanning electron microscopy (SEM) attached to the energy-dispersive X-ray (EDX) module. The chemical compositions and oxidation states of the elements in ZnCo.sub.2-xMo.sub.xO.sub.4 were studied using an X-ray photoelectron spectroscopy (XPS) instrument, where CIs peak at 284.8 eV is used as a reference to calibrate the XPS spectra. The first-principles calculations were conducted using the density functional theory (DFT) using DFT-based Quantum ATK software.

Example 4: Electrochemical Procedure

(80) A three-electrode cell Metrohm AutoLab PGSTAT302N potentiostat in 1.0 molar (M) potassium hydroxide (KOH) electrolyte with a pH of 13.6 was used to evaluate the hydrogen evolution reaction (HER) performance of the ZnCo.sub.2-xMo.sub.xO.sub.4 (x0.10) electrocatalyst. The working electrode was a 3 millimeters (mm) diameter glassy carbon (GC) electrode. Silver/silver chloride (Ag/AgCl) (3.5 M potassium chloride (KCl) solution) and platinum were used as reference electrodes and counter electrodes in the chemical cell. The electrolyte was bubbled with nitrogen (N.sub.2) for 30 minutes before the electrochemical measurements. In the case of ZnCo.sub.2-xMo.sub.xO.sub.4 (x=0.06), the surface of the GC working electrode was modified with the electrocatalyst by drop casting 10 microliters (L) of an ink and drying them at room temperature for 3 hours in a fume hood to achieve a catalyst loading of 0.285 milligrams per square centimeter (mg cm.sup.2). The ink was prepared by dispersing 4.0 milligrams (mg) of material in a 1.0 mL mixture of 80% water and 20% ethanol with 80 microliters (L) of Nafion solution (5 wt. %), which was then ultrasonicated for 30 minutes. Further, the catalytic performance of the electrodes was evaluated using linear sweep voltammetry (LSV) with a scan rate of 5 millivolts per second (mV s.sup.1) in 1.0 M KOH solution. The measured voltage was adapted to the reversible hydrogen electrode (RHE) by using the below-mentioned equation:
E.sub.RHE=E.sub.applied.sup.0+0.0591pH+E.sub.Ag/AgCl
The Tafel slopes were calculated according to the below mentioned Tafel equation.
(=+b log(j))

(81) Electrochemical impedance spectroscopy (EIS) measurements were performed from 10.sup.1 (hertz) Hz to 10.sup.5 Hz with 10 millivolt (mV) amplitude using the same Autolab: PGSTAT302N potentiostat equipped with a FRA32 M module. The electrochemically active surface area (ECSA) of the representative electrodes was calculated by measuring a cyclic voltammetry (CV) in a non-faradic region (0.21 to 0.31 V.sub.Ag/AgCl) at different scan rates (40, 60, 80, 100, 120, 140, 160, and 180 mV s.sup.1). The difference in current density variation (j=j.sub.aj.sub.c) at an applied potential of 0.28 V.sub.RHE was plotted against the scan rate to estimate the electrochemical double-layer capacitance (C.sub.dl), which was further used to calculate the ECSA. The ECSA of the representative electrodes were evaluated by the below mentioned equation.
A.sub.ECSA=C.sub.dl/C.sub.s
where specific capacitance (C.sub.s)=0.04 microfarad per square centimeter (mF cm.sup.2).
Further, the roughness factor was calculated using the below mentioned equation.
RF=ECSA/A.sub.geomatric.
Furthermore, the specific activity (SA) in milliamperes per square centimeter (mA cm.sup.2) was calculated by ECSA using the below mentioned equation.
SA=j/ECSA
where j is the cathodic current at an overpotential of 300 millivolts (mV). The surface-active sites (N) of the represented electrodes were evaluated by measuring the CV at 60 millivolts per second (mV s.sup.1) in 1.0 molar (M) potassium hydroxide (KOH) electrolyte solution. The integrated charge of each electrode was divided by 2 by assuming a one-electron redox process to obtain surface charge density (Q.sub.S). The value of N was computed by below mentioned equation.
N=Q.sub.S/F

(82) The exchange current density (I.sub.ex) values of representative electrodes were determined. Chronoamperometric measurements were performed at a current density of 10 mA cm.sup.2 and 50 mA cm.sup.2 to assess the stability and durability of the ZnCo.sub.2-xMo.sub.xO.sub.4 (x=0.06) electrode. The linear sweep voltammetry was repeated for 1000 cycles to evaluate the cyclic performance of the electrodes.

Example 5: Phase Analysis

(83) The cryptography analysis of the composition and purity of the catalysts ZnCo.sub.2-xMo.sub.xO.sub.4 (x0.10) and bare ZnCo.sub.2O.sub.4 were characterized through an X-ray powder pattern using an X-ray diffractometer (XRD) as shown in FIG. 2A and FIG. 2B. The XRD pattern exhibited the characteristic peaks of cubic ZnCo spinel oxide (ZnCo.sub.2O.sub.4) without undesired phase or external change. The small crystal size of all the samples was confirmed by the broadened peaks. Further, the shifts of the most intense peak (311) toward the lower angle led to an increase in the lattice parameters. These findings confirmed the effectively synthesized ZnCo. The lattice parameters, crystal size, and cell volume Rietveld referment fitting utilizing Match 3 and the data are listed in Table 1. As seen from Table 1, value lattice parameters (a) increase with the increase in Mo ratio. This is due to the expansion in lattice caused by the difference in ionic radii between Mo and Co. The crystallite size, which was found out using Scherrer's equation, showed slight variation when the Mo amount is increased in the 10 nanometers (nm) to 14 nm range. Further, the cation distribution of the ZnMo.sub.xCo.sub.2-xO.sub.4 spinel system was determined using the Bertaut method based on X-ray diffraction. The ratios of XRD intensities from the I.sub.220/I.sub.440 and I.sub.422/I.sub.400. Due to the sensitivity to cation distribution, crystallographic planes were utilized in the calculations. The resulting cation distribution for ZnMo.sub.xCo.sub.2-xO.sub.4 is provided in Table 1. It is known that Co ions exist in both 3.sup.+ and 2.sup.+ oxidation states to maintain the stoichiometry of the compound. Most Co ions are situated in octahedral sites, while Zn ions primarily occupy the tetrahedral A-sites. With the introduction of Mo ions, the percentage of Co ions decreased, and the rare-earth Mo ions occupied the octahedral B-sites.

(84) TABLE-US-00001 TABLE 1 Structural parameters of ZnCo.sub.2-xMo.sub.xO.sub.4 (x 0.10). D.sub.XRD Cation distribution x a () V (.sup.3) (nm) 0.03 .sup.2 R.sub.Bragg Tetrahedral A-site Octahedral B-site 0.00 8.1167 534.7368 12.4 1.0 10.7 Zn.sub.0.9Co.sub.0.1 Zn.sub.0.1Co.sub.1.9 0.02 8.1176 534.9049 11.8 3.2 35.8 Zn.sub.0.9Co.sub.0.1 Zn.sub.0.1Mo.sub.0.02Co.sub.1.88 0.04 8.1177 534.9246 12.5 1.4 27.0 Zn.sub.0.9Co.sub.0.1 Zn.sub.0.1Mo.sub.0.04Co.sub.1.86 0.06 8.1319 537.7526 14.5 1.5 32.8 Zn.sub.0.9Co.sub.0.1 Zn.sub.0.1Mo.sub.0.06Co.sub.1.84 0.08 8.1458 540.5029 10.3 1.3 31.6 Zn.sub.0.9Co.sub.0.1 Zn.sub.0.1Mo.sub.0.08Co.sub.1.82 0.10 8.1616 543.6582 11.1 1.6 31.3 Zn.sub.0.9Co.sub.0.1 Zn.sub.0.1Mo.sub.0.1Co.sub.1.8

Example 6: Morphological Analysis

(85) The surface morphology and elemental composition of ZnCo.sub.2-xMo.sub.xO.sub.4 (x=0.06) were analyzed with SEM and high-resolution transmission electron microscopy (HR-TEM), as illustrated in FIGS. 3A-3C and FIGS. 4A-4C. FIGS. 3A-3C show the different magnifications of SEM images, which illustrates the uniform growth of the 3D structure of highly agglomerated spherical particles with sizes around 2 micrometers (m) to 5 m. The spherical particles, including well-aligned nanoneedles, were observed in the high-magnification images. This type of morphology is used to penetrate the electrolyte to provide higher transportation for HER with a reduction of the energy necessitated to split the HO bond. The EDX analysis of ZnCo.sub.2-xMo.sub.xO.sub.4 (x=0.06) was presented in FIG. 4A and the spectrum shows the existence of Zn, Mo, Co, and O elements. These results indicate that the EDX spectrum contains only relevant peaks related to the materials. No extra peaks were observed for contaminates, which confirms the purity of the prepared materials. Furthermore, FIG. 4B and FIG. 4C show the TEM and HR-TEM of ZnCo.sub.2-xMo.sub.xO.sub.4 (x=0.06) illustrating the formation of nanoneedles. Furthermore, the interplanar spacings and the lattice fringes distance at 0.16, 0.18, and 0.24 nm corresponding to (422), (331), and (311) shown by the HR-TEM image are calculated. The derived results are consistent with that of the XRD results observed in FIG. 2A-2B.

Example 7: XPS Analysis

(86) X-ray photoelectron spectroscopy (XPS) was employed to examine the chemical bonding and oxidation state of each element in ZnCo.sub.2-xMo.sub.xO.sub.4 over a broad range of energy spectrums to verify the existence of Co, Zn, Mo, and O, as shown in FIG. 5A. To further confirm the chemical state, the high-resolution spectra of each element were acquired by rescanning in a narrow energy range. FIG. 5B shows the core spectra of Co 2p. It exhibits two major peaks at Co 2p.sub.3/2 and Co 2p.sub.1/2 at 779.3 electron volt (eV) and 794.4 eV, along with the satellite peaks at 788.8 eV and 803.6 eV. The deconvolution of Co 2p spectra presented two characteristic peaks. The peaks at 779.2 eV and 794.2 eV are attributed to the Co.sup.2+ state, while peaks at 780.6 eV and 795.5 eV are attributed to the Co.sup.3+ state. This indicates the presence of Co atoms at octal and tetrahedral sites in the spinel structure. FIG. 5C exhibits the core spectra of Mo 3d arising from the spin-orbit coupling of 3d.sub.5/2 and 3d.sub.3/2 states corresponding to the binding energy of 232.0 eV and 235.1 eV, respectively, along with a satellite peak at 237.0 eV. The core spectra of Zn 2p.sub.3/2 and Zn 2p.sub.1/2 were observed at 1020.3 eV and 1043.4 eV, as shown in FIG. 5D. The deconvolution did not introduce any new peak of other oxidation states of Zn and confirmed the presence of Zn in the 2.sup.+ oxidation state, partially occupying the tetrahedral sites in the spinel structure. The O 1s core level spectrum was observed and presented in FIG. 5E. The deconvolution provided three characteristic peaks at 529.8 eV, 531.3 eV, and 533.0 eV corresponding to the metal-oxygen bonding in cobaltite structure, oxygen defects in the spinel matrix, and surface hydroxyl groups, respectively. The defected oxygen in the spinel matrix may enhance the HER performance.

Example 8: Electrochemical Performance

(87) The electrochemical performance of the representative bare and ZnCo.sub.2-xMo.sub.xO.sub.4 (x0.10) electrodes was evaluated by performing linear sweep voltammetry (LSV) and chronopotentiometry (CP) in three-electrode system in a N.sub.2-saturated 1.0 M KOH solution (pH=13.6). FIG. 6A shows the LSV curves obtained at a 5 mV s.sup.1 scan rate. After the GC electrode was ZnCo.sub.2O.sub.4 modified, the current was enhanced to 10 mA cm-2 and an overpotential of 0.37 V.sub.RHE was reached. Further, the catalytic activity was enhanced after Mo doping to the Co sites in ZnCo.sub.2O.sub.4, forming ZnCo.sub.2-xMo.sub.xO.sub.4. Doping with high valence elements such as Mo.sup.6+ into the metal alloyed oxides might adjust the electronic structure, thereby increasing the withdrawal of electrons for Mo.sup.6+ to enhance the active sites for HER activity. Thus, incorporating Mo.sup.6+ in the ZnCo.sub.2O.sub.4 matrix tunes the electronic structure of Co in the matrix, thereby improving the HER activity and efficiency by providing more catalytic centers. As shown in FIG. 6B, the synthesized ZnCo.sub.2-xMo.sub.xO.sub.4(x=0.06) electrode exhibits the best HER catalytic activity with low overpotential of 195 mV and 280 mV to achieve the current density of 10 mA cm.sup.2 and 50 mA cm-2 respectively, which is higher than other ZnCo.sub.2-xMo.sub.xO.sub.4 and bare ZnCo.sub.2O.sub.4 electrodes. Further, the hydrogen evolution kinetics of bare and Mo-doped ZnCo.sub.2O.sub.4 electrodes was explored by a linear fit of the Tafel plot in a Tafel slopes for the overpotential (f) versus the log of current density. FIG. 6C shows the Tafel slope of 6% Mo-doped ZnCo.sub.2O.sub.4 electrode had 81.4 millivolts per decade (mV dec.sup.1), which is smaller than other compositions of Mo-doped and bare ZnCo.sub.2O.sub.4 electrodes. This demonstrates that 6% Mo-doped ZnCo.sub.2O.sub.4 is more favorable and faster reaction kinetics than other compositions of Mo-doped and bare ZnCo.sub.2O.sub.4 electrodes. However, the Tafel slope was again increased for 8% and 10% Mo-doped ZnCo.sub.2O.sub.4 electrodes, for the suppressed active sites and consistent with the LSV curves in FIG. 6A.

(88) The electrochemical active surface area (ECSA) was further investigated to explore the intrinsic HER activity of bare and Mo-doped ZnCo.sub.2O.sub.4 electrodes. ECSA is calculated by measuring the double-layer capacitance (C.sub.dl), which was assessed by measuring cyclic voltammetry at different scan rates within a non-faradic region, as shown in in FIG. 7A. The CVs are measured from 0.21-0.31 V.sub.Ag/A.sub.gCl at different scan rates from 40 to 180 mV s.sup.1 in 1.0 M KOH solution. The ZnCo.sub.2-xMo.sub.xO.sub.4(x=0.06) electrode exhibits the largest C.sub.dl value of 0.386 mF cm.sup.2 among other ZnCo.sub.2-xMo.sub.xO.sub.4 and bare ZnCo.sub.2O.sub.4 electrodes, as shown in FIG. 7B. This C.sub.dl value of ZnCo.sub.2-xMo.sub.xO.sub.4 (x=0.06) electrode is four times higher than that of bare ZnCo.sub.2O.sub.4 electrode, which indicates the significance of Mo doping in the ZnCo.sub.2O.sub.4 matrix. Accordingly, the ZnCo.sub.2-xMo.sub.xO.sub.4 (x=0.06) electrode exhibits a significantly higher ECSA of 9.65 cm.sup.2 as compared to that od bare ZnCo.sub.2O.sub.4 electrode of 2.63 cm.sup.2 and other Mo-doped ZnCo.sub.2O.sub.4 electrodes as illustrated in the histogram of ECSA as shown in FIG. 7C. Further, doping of Mo prevents the surface oxidation of ZnCo.sub.2O.sub.4 and exposes more active sites to enhance the HER process. However, excessive doping of Mo in ZnCo.sub.2O.sub.4 may cause structure and composition changes which may lead to suppression of the active sites and may act as a recombination center. These findings are consistent with the LSV results in FIG. 6A. To further exclude the effect of surface area on catalytic performance, the LSV curves were normalized against ECSA, as shown in FIG. 8A and FIG. 8B. The ZnCo.sub.2-xMo.sub.xO.sub.4 (x=0.06) electrode still exhibits higher HER activity, which indicates that Mo doping significantly improves intrinsic properties, and enhances the catalytic HER activity. Further, the active sites (N) of the catalyst of represented electrodes were calculated from surface charge density (Q.sub.S), and it was found that ZnCo.sub.2-xMo.sub.xO.sub.4(x=0.06) electrode of 0.22 coulomb per square centimeters (C cm .sup.2) exhibited higher surface charge density as compared to bare and other Mo-doped ZnCo.sub.2O.sub.4 electrodes. As shown in FIG. 8C, a higher number of active sites 2.2878210.sup.6 mol cm.sup.2 compared to bare and Mo-doped ZnCo.sub.2O.sub.4 electrodes are noticed, thereby enhancing the HER process. This result is consistent with the LSV, Tafel plot, and ECSA of the representative electrodes. The specific activity (SA) was measured after ECSA and normalized to the current density at 0.3 V in 1.0 M KOH. As shown in FIG. 7D, the volcano plot was observed where ZnCo.sub.2-xMo.sub.xO.sub.4(x=0.06) electrode exhibited higher SA than bare and other Mo-doped ZnCo.sub.2O.sub.4 electrodes. This shows that the ZnCo.sub.2-xMo.sub.xO.sub.4(x=0.06) electrode possesses the largest active surface area and thus enhances the HER activity, which is consistent with the LSV, and Tafel slope.

(89) The electrical impedance spectroscopy (EIS) measurements were also performed to confirm the higher catalytic activity of ZnCo.sub.2-xMo.sub.xO.sub.4 (x=0.06) electrode than those of bare and other Mo-doped ZnCo.sub.2O.sub.4 electrodes. The Nyquist plot of bare, and Mo-doped ZnCo.sub.2O.sub.4 electrodes was measured at 0.3 V.sub.RHE potential to evaluate the charge transfer kinetics at the semiconductor electrolyte interface (SEI). FIG. 9A shows the typical semicircles for bare, and Mo-doped ZnCo.sub.2O.sub.4 electrodes that were observed and fitted with the equivalent circuits. R.sub.s shows the solution and connection resistance, while R.sub.ct and C.sub.s represent the SEI charge transfer resistance and capacitance. Table 2 exhibits the fitted parameters of the representative electrodes at 0.3 V.sub.RHE potential in an alkaline solution. FIG. 9B shows the histogram of R.sub.ct values of the representative electrodes, where bare ZnCo.sub.2O.sub.4 showing higher R.sub.ct of 3120 ohms (), indicating that that of the bare electrodes. The Mo-doped ZnCo.sub.2O.sub.4 electrodes exhibit lower charge transfer resistance than the bare ZnCo.sub.2O.sub.4 electrode. As shown in FIG. 9B and table 2, the ZnCo.sub.2-xMo.sub.xO.sub.4 (x=0.06) electrode illustrates the lowest R.sub.ct of 85 than other Mo-doped ZnCo.sub.2O.sub.4 electrodes, which indicates that a faster charge transfer rate was observed at SEI, thus enhancing the HER process. Furthermore, the exchange current density (I.sub.ex) was calculated to estimate the reflection of the intrinsic activity of the catalysts and the effect of R.sub.ct during HER. As shown in FIG. 9C the I.sub.ex value of ZnCo.sub.2-xMo.sub.xO.sub.4 (x=0.06) of 2.13 mA cm.sup.2 was higher than that of other Mo-doped compositions of ZnCo.sub.2O.sub.4 electrodes and bare ZnCo.sub.2O.sub.4 electrode. This indicates that the ZnCo.sub.2O.sub.4 electrodes exhibit lower resistance across the SEI, and a rapid electron transfer process was observed during the electrocatalytic process. The lower R.sub.ct and higher I.sub.ex values of ZnCo.sub.2-xMo.sub.xO.sub.4 (x=0.06) are consistent with the LSV and ECSA. An equivalent circuit used to fit the Nyquist plot of ZnCo.sub.2-xMo.sub.xO.sub.4 (x0.10) electrocatalyst is depicted in FIG. 9D.

(90) TABLE-US-00002 TABLE 2 Comparison of fitted parameters from Nyquist plot for bare and ZnCo.sub.2-xMo.sub.xO.sub.4 (x 0.10) electrodes used for electrochemical HER performance. R.sub.s R.sub.ct Q.sub.S x 1 10.sup.5 F N .sup.2 0.00 7.7 3119.6 5.5 0.902 0.015 0.02 6.8 699.1 12.1 0.888 0.078 0.04 7.1 162.1 21.3 0.854 0.071 0.06 8.1 85.3 20.6 0.852 0.108 0.08 5.4 216.2 15.4 0.866 0.086 0.10 6.2 360.8 18.3 0.846 0.038

(91) In addition to the catalytic activity, durability, and long-term stability, especially at high current density, chronopotentiometry (CP) is essential for an advanced electrocatalyst. ZnCo.sub.2-xMo.sub.xO.sub.4 (x=0.06) electrocatalyst shows good operational stability on catalytic performance. An accelerated degradation test was used to confirm the stability of the 6% Mo-doped ZnCo.sub.2O.sub.4 electrocatalyst by measuring continuous 1000 LSV cycles. The 1.sup.st and the 1000.sup.th cycle LSV of ZnCo.sub.2-xMo.sub.xO.sub.4 (x=0.06) electrode show the same LSV measurement, except for a 10 mV difference, which might be attributed to the bubble formation on the surface of the electrode and u enhance the overpotentials as shown in FIG. 10A. The 10 mV change in the potential is due to the robust stability of the material. Furthermore, a CP test was performed on ZnCo.sub.2-xMo.sub.xO.sub.4 (x=0.06) electrocatalyst at applied potentials from 10, 20, and 50 mA cm.sup.2 for brief time intervals as shown in FIG. 10B, and the curve was consistent with the LSV curve. The instant response and constant potential of each step was attributed to a favorable mass transportation ability and strong robustness of ZnCo.sub.2-xMo.sub.xO.sub.4 (x=0.06) electrocatalyst. For practical applications, the long-term stability of the electrode is important in evaluating the electrode. FIG. 10C shows the long-term CP measurement of the ZnCo.sub.2-xMo.sub.xO.sub.4 (x=0.06) electrode performed at the constant current density of 50 mA cm.sup.2. After a 40 hours of continuous CP experiment, the potential was suppressed by 11 mV, and the suppressed factor was only 3%. During CP measurements, any range fluctuation which is due to continuous bubble formation and removal at the surface of the electrocatalyst surface was recorded. However, the ZnCo.sub.2-xMo.sub.xO.sub.4 (x=0.06) electrocatalyst exhibits excellent catalytic activity by retention of the potential for 40 hours as shown in FIG. 10C. FIG. 10D shows the Nyquist plot measured for ZnCo.sub.2-xMo.sub.xO.sub.4 (x=0.06) electrocatalyst at 0.3 V.sub.RHE after the stability test. The semicircle diameter observed in FIG. 10D shows that a small fluctuation was observed after the stability test. Further, The R.sub.et value for ZnCo.sub.2-xMo.sub.xO.sub.4(x=0.06) electrocatalyst after the stability test reached 96, which is just 11 higher than the value observed before the stability test of 85. This shows that ZnCo.sub.2-xMo.sub.xO.sub.4(x=0.06) electrocatalyst exhibits no change in charge transfer resistance at the electrode-electrolyte interface during the HER process, making ZnCo.sub.2-xMo.sub.xO.sub.4 (x=0.06) electrocatalyst a superior electrocatalyst for HER. Moreover, the Tafel slope is used to validate the HER mechanism and reaction-rates determining stages. The Volmer, Heyrovsky, and Tafel processes are the most common routes for converting atomic H into H molecules. A combination of the Volmer process with Tafel or Heyrovsky may lead to the creation of molecular hydrogen. The rate-determining stage is followed by the Volmer mechanism when the slope value is around 120 mVdec.sup.1. The rate-determining stage is deemed to be followed by either the Heyrovsky or Tafel mechanism when the slope value is around 40 or 30 mVdec.sup.1, respectively. The present findings of the Tafel slope (81.4 mVdec.sup.1) for ZnCo.sub.2-xMo.sub.xO.sub.4 (x=0.06) electrocatalysts clearly indicated that the rate-determining stage was due to the Volmer-Heyrovsky mechanism.

(92) The post-HER stability of the ZnCo.sub.2-xMo.sub.xO.sub.4 (x=0.06) electrode was examined by measuring XRD as shown in FIG. 11A, and the results are consistent with the XRD results observed in FIGS. 2A and 2B. No change in the structure and composition was observed after long-term stability test. Moreover, the morphology of ZnCo.sub.2-xMo.sub.xO.sub.4 (x=0.06) after a stability test exhibited a microsphere with broken nanoneedles, as shown in FIG. 11B, which indicates that ZnCo.sub.2-xMo.sub.xO.sub.4 (x=0.06) electrocatalyst is a stable electrocatalyst and may be suitable for hydrogen fuel cell applications and industries.

Example 9: Density Functional Theory Calculations

(93) By Using first-principles calculations within the density functional theory (DFT), numerical calculations were implemented to explain the influence of Mo dopants on the catalytic and HER activity. The structures are designed were examined using DFT-based QuantumATK software. The relevant characteristics were revealed by (i) hydrogen (H) and (ii) water (W) molecules adsorbed on the surface of both pristine surface organometallic chemistry (PSOMCs) and Mo-doped ZnCo.sub.2O.sub.4 surface organometallic chemistry (MSOMCs). The following atomic configurations were employed: H and W adsorbed on the surface of (i) PSOMCs (PSOMCs-H and PSOMCs-W, respectively), (ii) MSOMCs with 1.8% Mo content (MSOMCs-H.sup.I and MSOMCs-W.sup.I, respectively), (iii) MSOMCs with 3.6% Mo concentration (MSOMCs-H.sup.II and MSOMCs-W.sup.II, respectively). The structure of PSOMCs was designed to employ a unit cell composed of 56 atoms (8 Zn, 16 Co and 32 O atoms), with the below lattice parameters.
A=11.409
B=5.705
C=20.067
A periodic-slab structure was utilized for the infinite PSOMCs (100) surface, which is perpendicular to z-axis (C), leading to non-periodicity in the direction of C due to the vacuum layer (with a thickness around of 15 ) added right above the surface. Two representative unit cells, showing H and W molecules on the surface (MSOMCs-H.sup.I and MSOMCs-W.sup.I), are depicted in FIG. 12A & FIG. 12. To optimize the individual atomic distances within the accompanying unit cells, representing doped structures, the force tolerance was set to 0.01 eV/. For the exchange and correlation potential, spin-resolved generalized gradient approximation (SGGA) with Perdew-Burke-Ernzerhof (PBE) functional (SGGA.PBE) was adopted. The SGGA was applied as it may adequately describe the distribution of ions in the associated nanoparticles. The atomic cores were represented by PseudoDojo pseudopotentials. The identification of the electronic structure of valence electrons (Zn: 4s.sup.23d.sup.10, Co: 4s.sup.23d.sup.7, Mo: 5s.sup.14d.sup.5, O: 2s.sup.22p.sup.4) was fulfilled by the medium basis sets of local numerical orbitals. A k-point sampling of (3,5,1) was chosen with a mesh cutoff energy of 125 Hartree.

(94) The chemical reactivity and HER activity on the catalyst surfaces involves (i) water adsorption and dissociation, and (ii) H adsorption and desorption. Substitutional dopants may improve the reactivity and HER activity The catalytic activity was investigated through the water molecules, which were adsorbed on the surface of the catalysts. The relevant adsorption energy (E.sub.A) of water molecules was computed using the below-mentioned equation
E.sub.A=E.sub.systemE.sub.slabE.sub.W
where E.sub.system is the total energy of the nanoparticles, E.sub.slab stands for the energy without water, and E.sub.W denotes the energy of water molecules. The adsorption energy implies the interaction between the surface and molecules right above it. A positive adsorption energy refers to unstable adsorption. On the other hand, a negative E.sub.A indicates an exothermic process and allows the molecules to adsorb on the slab surface. The more negative E.sub.A is, the more favorable ihe molecule adsorption. During the process of molecule adsorption, the strength of the adsorption energy determines the types of adsorption mechanisms. A lower negative E.sub.A indicates a physisorption while a higher negative E.sub.A indicates chemisorption. These mechanisms are related to the altered bond lengths and charge transfer. The water adsorption energies are respectively calculated to be 2.32 eV (53.61 kcal/mol), 2.40 eV (55.23 kcal/mol), and 2.47 eV (57.03 kcal/mol) for the PSOMCs-W, MSOMCs-W.sup.I, and MSOMCs-W.sup.II. As the most negative E.sub.A was exhibited by MSOMCs-W.sup.II, MSOMCs-W.sup.II may have the highest stability and reactivity in water adsorption. The Mo dopants substituting for the Co ions in MSOMCs-W.sup.II are responsible for the highest catalytic activity. The corresponding dissociation of water molecules is related to the strength of the interaction with the surface atoms in a slab. Due to the reactivity and adsorption energy of Mo-doped ZnCo.sub.2O.sub.4 nanostructures, Mo-doped ZnCo.sub.2O.sub.4 may be used as catalysts.

(95) TABLE-US-00003 TABLE 3 E.sub.A.sup.H and G.sup.H values for the PSOMCs-H, MSOMCs-H.sup.I and MSOMCs-H.sup.II. System E.sub.A.sup.H (eV) G.sup.H (eV) PSOMCs-H 2.73 0.38 MSOMCs-H.sup.I 2.72 0.37 MSOMCs-H.sup.II 2.70 0.35

(96) FIG. 12A and FIG. 12B show the HER activity examined through the H atoms adsorbed on the surface. G.sup.H plays a significant role in exposing the HER activity of catalysts. Gibb's free energy of H adsorption (G.sup.H) was determined. G.sup.H is proportional to hydrogen adsorption energy (E.sub.A.sup.H), which may be computed with the help of total energy, zero-point energy and entropy term. The equation is as below.
G.sup.H=E.sup.H+0.24eV
where E.sup.H stands for the hydrogen chemisorption energy. Both the values of E.sub.A.sup.H and G.sup.H are listed in Table 3. The E.sub.A.sup.H (G.sub.H) energies were calculated to be 2.73 eV (0.38 eV), 2.72 eV (0.37 eV), and 2.70 eV (0.35 eV) for the PSOMCs-H, MSOMCs-H.sup.I, and MSOMCs-H.sup.II, respectively. The G.sup.H values obtained in the present work agreed with earlier results on iron oxide-based nanocomposites and various metals including Mo. Possessing a suitable G.sup.H is vital for the HER process. Efficient HER activity is exhibited by negative G.sup.H values closer to zero. A positive G.sup.H implies diminishing of H adsorption on the catalyst. In contrast, a negative G.sup.H shows the enhancement of H molecules on the surface. As a result, of all the structures, MSOMCs-H.sup.II may be the most efficient catalyst for HER activity. This result confirms the improvement of chemical activity with Mo dopants as the highest catalytic activity due to water also exhibited by the same Mo-doped slab (MSOMCs-W.sup.II). This is due to the accompanying interaction and charge transfer due to hybridization of orbitals. It was already reported that Mo dopants could improve the HER performance of ZnIn.sub.2S.sub.4 structures and CoP nanoarrays. Comparing the E.sub.A.sup.H and G.sub.Hvalues demonstrates that a higher H adsorption energy yield may minimize the HER activity. Thus, the efficiency of the catalysts is also related to the strength of the H adsorption energy.

(97) The impact of Mo dopants on the spin-resolved electronic structure characteristics of PSOMCs-H, MSOMCs-H.sup.I, and MSOMCs-H.sup.II are revealed by the spin-dependent density of states DOS.sub. (FIG. 13A) and partial density of states (PDOS.sub.) projected onto the Mo atoms. (FIG. 13B) The DOS.sub. spectra around the Fermi energy (E.sub.F, which is set to zero) where spin-up () states represent positive variations and spin-down () states represent negative variations. A spin asymmetric behavior observed in the spectra implies magnetism arising from transition metals' spin-split d-band electrons. The Mo dopants tune the spin-resolved electronic structure characteristics of PSOMCs-H. An energy gap starting at around 2.5 eV vanishes when the Mo atoms are doped, as shown in FIG. 13A. The PDOS.sub. in FIG. 13B, projected onto the Mo dopants shows the contribution of Mo atoms in each slab to the electronic states. Further FIG. 13B demonstrates the spin asymmetric spectra due to Mo dopants. It reflects that magnetism and accompanying charge transfer may be adjusted by Mo dopants at particular sites. The charge transfer may be presented with Mulliken analysis. The corresponding electron density may be visualized by the mesh cut-off and exposing the density grid sampling. FIGS. 13C-13D shows how adding Mo dopant leads to the adjustment of electron distribution for the representative PSOMCs-W and MSOMCs-W.sup.I structures.

(98) ZnCo.sub.2-xMo.sub.xO.sub.4 (x0.10) was prepared by hydrothermal route combined with a post-annealing process and evaluated as HER electrocatalysts. The structural analysis and TEM analysis confirmed the presence of cubic ZnCo.sub.2O.sub.4 spinel oxide. The nano-microsphere morphology of ZnCo.sub.2-xMo.sub.xO.sub.4 (x0.10) was shown by FE-SEM results. The successful incorporation of Mo into the ZnCo.sub.2O.sub.4 was confirmed by XPS analysis. When the Mo content was increased, the ZnCo.sub.2-xMo.sub.xO.sub.4 exhibited an inverted volcano-like trend in HER overpotentials and Tafel slopes. Systematic comparison of the catalytic activity of ZnCo.sub.2-xMo.sub.xO.sub.4 reveals that 6% Mo doped ZnCo.sub.2O.sub.4 electrocatalyst is highly efficient for HER and exhibits the best HER performance, such as small overpotential (195 mV at 10 mA cm.sup.2) and Tafel slope (81.4 mV dec.sup.1). Further, the 6% Mo-doped ZnCo.sub.2O.sub.4 exhibited higher double-layer capacitance and abundant surface-active sites, thereby reducing the overpotential and improving the HER process. The EIS further confirmed the higher charge transfer kinetics by ZnCo.sub.2-xMo.sub.xO.sub.4 (x=0.06) electrocatalysts. the durability and stability of ZnCo.sub.2-xMo.sub.xO.sub.4 (x=0.06) electrocatalysts were confirmed by 1000 cycles of LSV followed by 40 hours of long-run stability test. Furthermore, the composition of bimetallic cobalt-based spinel oxide electrocatalysts may be tuned for HER application. The density of state spectra showed that Mo atoms may adjust the electronic structure characteristics of Mo-doped ZnCo.sub.2O.sub.4 nanoparticles. DFT calculations showed that, the most negative water adsorption energy is exhibited by the MSOMCs-Wu, showing the highest stability, reactivity, and catalytic activity due to water adsorption. The slab structure MSOMCs-W.sup.II adsorbed by hydrogen may be the most efficient catalyst due to HER activity. The catalytic and HER activity may be improved by Mo concentration. Due to the reactivity and adsorption energy of Mo-doped ZnCo.sub.2O.sub.4 nanostructures, Mo-doped ZnCo.sub.2O.sub.4 may be incorporated in many catalytic applications.

(99) Numerous modifications and variations of the present disclosure are possible in light of the above teachings. It is therefore to be understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described herein.